Cement grinding aid and pack set inhibitor

ABSTRACT

Additive compositions for use as grinding aids and pack set inhibitors in the manufacture of hydraulic cement composed of a water-soluble polyol, particularly a glycol, and a water-soluble salt of an aliphatic acid having no more than three carbons, said additive compositions being used either alone or in combination with water-soluble salts of a sulfonated lignin, a water-soluble hydroxyalkyl amine and urea, the hydraulic cement product of this addition and the method for making the cement product.

AU 1 l 2 Ex United States Patent lnventors Howard II. Moorer Charleston;Charles M. Anderegg, Sullivan's Island, both oi S.C.

Appl. No. 702,519

Filed Feb. 2, 1968 Patented Oct. 26, 1971 Assignee West Virginia Pulpand Paper Company New York, N.Y.

CEMENT GRINDING AID AND PACK SET INHIBITOR 12 Claims, No Drawings US. (I106/90, l06/3l4, 106/315 ht. C04b 13/26 Field of Search 106/314,

References Cited UNITED STATES PATENTS 3,385,792 5/1968 Monvay 252/423,2l 1,675 l0/l965 Johnson 106/87 2,487,080 1 H1949 Swenson 252/42Primary Examiner-Tobias E. Levow Assistant Examiner-W. T. ScottAuorneys- Robert S. Grimshaw and Ernest B. Lipscomb, Ill

CEMENT GRINDING AID AND PACK SET INHIBITOR This invention relates toadditive compositions for incorporation in hydraulic cements, forexample, Portland cements, the resultant hydraulic cement mixescontaining the additive compositions, and to the process for makingthese cements.

This invention relates more particularly to additive compositions foruse as grinding aids and pack set inhibitors in the manufacture ofhydraulic cements and to hydraulic cements containing thesecompositions.

Hydraulic cements are produced by calcining suitable raw materials,generally a mixture of calcareous and argillaceous materials, to producea sintered clinker." Of the hydraulic cements, Portland types are by farthe most important cements in terms of quantity produced. The clinker ismixed with small amounts of gypsum and ground, usually in some type ofball mill, to a finely divided state having a relatively large surfacearea to yield the finished cement. Grinding of the clinker consumessubstantial quantities of time and energy. it is common practice in thecement industry to employ grinding aids which increase the efficiency ofthe grinding operation thereby lowering the power required to grind aunit of cement and which decrease the plant investment either byincreasing the through put of a given grinding mill or by reducing thesize of mill needed to grind a given amount of cement. The addition of agrinding aid enables the mill to grind the clinker to a smaller sizewith less energy by prohibiting the buildup of a coating of finermaterial on the grinding media and walls of the mill by coating thenascent surfaces of the cement clinker. This coating of the cementclinker reduces the higher energy forces present on the nascent surface.Caution must be taken to prevent undue reduction of the surface forcesbecause the cement becomes excessively fluid.

After grinding, most cements become semirigid when compacted byvibrations and will not flow until considerable mechanical effort hasbeen applied to disintegrate the semirigid mass. The reduction in amountof energy necessary to initiate flow in cement is referred to as "packset inhibition. The pack set inhibition property is particularlyimportant in unloading the dry cement powder from storage silos and/orafter transportation of the cement in trucks, barges, and railroadhopper cars. The tendency to pack set is effectively inhibited by areduction in the high surface energy of the cement produced upongrinding.

it is, therefore, a primary object of this invention to provide additivecompositions for hydraulic cements which function as both grinding aidsand pack set inhibitors.

Accordingly, it is an object of this invention to provide a hydrauliccement, particularly a Portland cement, or other cementitiouscomposition containing an additive which functions as both a grindingaid and a pack set inhibitor.

it is another object of this invention to provide a process forincreasing the grinding efiiciency of and inhibiting the pack set ofhydraulic cement by the addition thereto of a small but effective amountof an additive without deleteriously affecting the desirable propertiesof the cement.

It has been found that by intergrinding with hydraulic cement smallquantities of an additive composed of a water-soluble polyol and awater-soluble salt of an aliphatic acid having no more than threecarbons unexpectedly produces a synergistic effect which increases thegrinding efficiency of the clinker and retards pack set of the cement tosuch a degree that neither can do alone. Only a small amount of additiveneed be used to achieve the desired results. When added to a Portlandclinker at addition rates below 0.005 percent based on the weight of thecement, the grinding efficiency and the pack set inhibition are notimproved and at addition rates above about 1.0 percent based on theweight of the cement, the improvement rates are not significant. Thepreferred range is, based upon an economically acceptable amount,generally 0.0l to 0.05 percent. One ounce of additive per barrel ofcement amounts to approximately 0.0l66 percent by weight of cement. Theadditive is most conveniently and usually prepared as a solution inwater and when interground with the clinker is mechanically dispersedover the nascent surfaces thus reducing the surface forces of the cementto such a desired state that the results show substantially improvedgrinding and reduced mill retention times as well as facilitatingsubsequent storage and/or transportation. The reason for employing theadditive as an aqueous solution is that only about l-ounce solids weightbasis is used per barrel. The aqueous solution enables the additive tobe diluted and therefore circulated quickly and evenly throughout thegrinding mill.

Various other additive agents for hydraulic cement mixes have been usedboth alone and in conjunction with grinding aids and as pack setinhibitors, to achieve results of a similar character or to modify otherproperties of the hydraulic cements, as required by their particularuse. However, the effects of combining known additive agents with theadditive compositions noted above, have been surprisingly andunpredictably greater than the sum of their individual effects. Theaddition to the above additive compositions of an amine accelerator,salts of sulfonated lignin and/or urea when added either individually orin combination produce desirable additional improvements. Thecombination of one or several of these additive agents produces a largevariety of tailoring grinding aids, the formulation to finally bedetermined by per formance desired and economics.

The polyols referred to for the purpose of this invention include thosealiphatic alcohols containing two or more hydroxy groups that arewater-soluble. By water-soluble, it is meant that at least 5 grams ofthe polyol will dissolve in I00 grams of water. it is important that thepolyol be completely water-soluble because the additive is mostconveniently used in an aqueous'solution. The polyols of this inventioninclude the watersoluble diols such as ethylene glycol, propyleneglycols. polyethylene glycols, polypropylene glycols, diethylene glycol,triethylene glycol, dipropylene glycol and tripropylene glycol,combinations of these glycols, their derivatives, and reaction productsformed by reacting ethylene and propylene oxide or polyethylene glycolsand polypropylene glycols with active hydrogen base compounds(polyalcohols, polycarboxylic acids, polyamines, or polyphenols). Otherglycols contemplated include neopentyl glycol, pentanediols,butanediols.)

and such unsaturated diols as butyne diols and butene diols. In additionto the diols, the triol, glycerol, and such derivatives as ethylene orpropylene oxide adducts make excellent grinding aids. Other higherpolyols may include pentaerythritol. Another class of polyhydroxyalcohols contemplated are the sugar alcohols. The sugar alcohols areobtained by reduction of carbohydrates and differ greatly from theabove-mentioned polyols. These polyols are considered useful as grindingaids. Of the sugar alcohols mannitol and sorbitol are preferred.Numerous other polyols which meet the requirements of being an effectivegrinding aid and pack set inhibitor when combined with the salt of analiphatic acid having no more tlian three carbons will occur to thoseskilled in the art and the hereinabove list is intended to beillustrative only.

The preferred polyols include the water-soluble dihydric alcohols(glycols). The preferred glycols are the monoand polyglycols of ethyleneand propylene. These glycols are preferred primarily because of theircost and their water solubility. The polyglycols of ethylene arewater-soluble at molecular weights at least as high as 20,000. Thepolyglycols of propylene, although giving slightly better grindingefi'iciency than the ethylene glycols, are completely water-soluble upto molecular weights of only about 1,000.

As the number of carbons in the alcohol chain increases the watersolubility tends to decrease thus limiting the available glycols. Forexample, polybutylene glycol having a molecular weight of about 500 isonly slightly soluble in water while polyethylene glycol of the samemolecular weight is infinitely soluble. in the practice of thisinvention mixtures of the polyols may be effectively used. Althoughcommercial grade polyols are generally preferred, crude grades aresometimes used because of their economic benefits. By crude grades, itis meant, the less refined mixtures of polyols obtained from commercialprocesses either from original production of the polyols or reclaimedfrom other manufacturing processes. The polyols when used alone doincrease grinding efficiency somewhat, but in the process the tendencyto pack set is greatly increased. The use of dihydroxy polyols (glycols)as grinding aids is well known in the art and their use is set forth inU.S. Pat. No. 2,225,146. However, it has been found the combinations ofpolyols with the water-soluble salts of aliphatic acids having no morethan three carbons produces a grinding aid that is more efficient than apolyol alone and effectively inhibits pack set at the same time.

The additives, therefore, contemplate in combination with a polyol thewater-soluble salts aliphatic acids of no more than three carbons, i.e.,acetic, formic, and propionic. Among examples of water-soluble saltswhich may be employed are salts of the alkali metals, alkaline earthmetals, ammonia, aluminum, cobalt, and iron. Numerous other salts ofaliphatic acids of no more than three carbons which are water-solublewill occur to those skilled in the art. The most commonly used andpreferable salts are the sodium and potassium salts of acetic acid. Highacetic acid concentrations with sodium tend to crystallize above 80percent solids. For this reason potassium acetate is used when highsolids concentrations are desired. The use of acetates as pack setinhibitors is well known (see U.S. Pat. No. 2,857,286); however, whenadded to the grinding mill an acetate, when used alone, has an adverseeffect on grinding. This effect is pointed out by U.S. Pat. No.3,094,425 which teaches the use of pack'set inhibiting amount of aceticacid in a grinding mill will impair rather than help grinding. As thefollowing examples will show, when combined with a water-soluble polyol,aliphatic acids and their water-soluble salts are more effective asgrinding aids than either the polyol or the salt of the aliphatic acidhaving no more than three carbons when used alone.

In addition to an additive of a water-soluble polyol and the salt of analiphatic acid having no more than three carbons it is preferable toinclude other additive agents which further increase the grindingefficiency and further inhibit pack set by adding to the synergisticeffect produced. One preferred additive agent is an accelerator such asthat disclosed in U.S. Pat. No. 2,031,621. This accelerator is awater-soluble hydroxyalkyl amine or a salt derivative thereof. The mosteffective of this class being triethanolamine. It is preferable to use acommercial grade which consists mostly of triethanolamine together withsmaller amounts of the primary and secondary amine. Other well-knownhydroxy-alkyl amine accelerators may also be successfully employed.

Another important class of additives are the water-soluble salts ofsulfonated lignin and sulfonated lignin derivatives. These lignins areprincipally obtained as byproducts from sulfite pulping of woodymaterials. The waste liquors from such pulping contain large quantitiesof lignin and lignin products in conjunction with other materials. Thesulfonated lignin additionally may be produced by reacting ligninsobtained from alkali pulping, acid hydrolysis or other known recoveryprocess with an inorganic sulflte, e.g., sodium sulfite, whcrebysulfonate groups are added to the lignin. For use in this invention, anyof the various watersoluble sulfonated lignins may be employed. It ispreferable, however, to utilize sulfonated lignins which are free ofcarbohydrate materials. Sulfonated lignins obtained from reaction ofsulfites with lignin do not contain any appreciable amounts of thesecarbohydrates and consequently may be employed as is. The sulfonatedlignins may be converted into water-soluble salts, and used as such, asdisclosed in U.S. Pat. No. 2,141,570. The use of sulfonated lignins ifadded to improve grinding serves to entrain air in the cement and toreduce the water required to give proper flow of the concrete mix.Further the low cost of these lignin salts makes a more economicalproduct.

Another addition to the product may be urea, which aids grindingefl'rciency. The urea when used in amounts up to about 5 percent of thesulfonated lignin material also increases the compressive strengths ofcement. However, urea may be used in larger amounts with other additiveswithout any deleterious effects on strength and set time.

The inclusion of each additive agent either individually or incombination serves to increase the grinding efficiency while inhibitingpack set and retaining other desirable properties of cement when addedto the grinding mill.

The term grinding aid describes an increase in production at constantproduct surface area or an increase in surface area at a constantproduction rate during the grinding of the clinker and gypsum in thefinish mill.

The pack set index is a relative term which numerically indicates theproclivity of a particular cement to pack set when it is stored in ortransported in bulk. The pack set index is obtained in the followingmanner: 100 grams of cement are placed in a 250-millimeter Erlenmeyerflask set on top of a variable vibrator. The flask containing the cementis vibrated for l5 seconds after which time it is removed from thevibrator and carefully placed in a jig with the axis of the flask lyinghorizontally. The flask is then rotated around its axis until thecompacted cement collapses. The flask is twisted by turning at 180angles at approximately 100 twists per minute. The number of 180 twistsrequired for the cement sample to collapse establishes the pack setindex. Thus, the greater the energy required to break up the bed, thehigher will be the pack set index. The pack set index obtained by thismethod correlates well with the field performance of the cement. Thehigher the pack set index of the particular cement, the more prone alarger volume of that cement is to pack set if maintained in bulk.

The practice of this invention may clearly be seen in the followingexamples.

EXAMPLE I Grinding Solids Composition Ratio ofGlycol to Aid Content, 1Acetate by Weight A 100.0 Propylene glycol B 99.2 Propyleneglycol-acetate :10 C ".0 Propylene glycol-acetate 60:40 D 77.7 Propyleneglycol-acetate 40:60 E 71.8 Propylene glycol-acetate 10:90

The above combinations were compared and the results in the table belowillustrate the effects of grinding and pack sci on the ground cement.The data in this table show a com arison of the invention compositionsto the blank as a plus or minus value of that blank.

Blaine fineness ter Compressh e sire ngth Air Pack 40 60 80 Conset 3 7I8 Additive min. min. min. tent index days days days A +533 +272 +2309.6 20.0 +75 +225 14] B +443 +192 +202 9.0 I75 200 C +316 +92 +2l2 8.510.2 -83 -15: -ll6 D +381 +362 +ll4 9.6 I0.8 -87 l01 I.U E +491 +282+237 9.6 ll.2 +8 58 9 Notes:

Blaine fineness (sq. cm/gm) by ASTM (204-55. Air content, percent byXSTM (18$ 59. Compressive strength in p.s.i. by ASTM (NW-M.

The surface area increases obtained with the glycol-acetate combinationsof this invention as compared to a blank and polypropylene glycolestablished that the combinations of the present invention improvedgrinding efficiencies to a markedly greater degree than the blank andwas slightly better than propylene glycol above a Blaine fineness ofabout 4,100 sq. cmJgm. The critical factor was that pack set inhibitionwas lost when propylene glycol alone was used. The pack set index of theblank was 12.2 and went sharply upward to 20 when propylene glycol alonewas used, but when the additive compositions of this invention (8through E) were used the pack set index was as low as 9.0. Also, anyloss in compressive strength was negligible and the air entrainment waswithin acceptable limits. The propylene glycol used was commerciallyobtained and was the most comparable of the glycols contemplated.

EXAMPLE n The data in the following table illustrate the efi'ects thatthe additive compositions of this invention have on the grinding ofcement clinkers and the inhibition of pack set on the ground cement andthe effects on mortars made therefrom. The data appearing in this tablewas obtained by testing individual batches of the same Portland-type Icement, each of which was prepared in the following manner; a 24-inchpilot ball mill containing steel balls graded from one-half inch to 2inches was heated to about 280' F; the additive was mixed directly withthe clinker at the rate of 1 ounce of additive per barrel of cement andthereafter the mix was charged to the mill. After rotating forpredetermined amounts of time, portions of the ground cement wereremoved. The fineness, pack set index and other properties of the groundcement were determined.

Blaine fineness, sq. cm/gn. by ASTM C204-55.

Air content in percent by ASTM C 185-59.

Compressive strength in p.s.i. by ASTM C 109-64. Commercial: acommercial additive-REAX 70A by West Virginia Pulp and .Paper Company.

Composition 8" of this invention, as identified in the table,

was prepared in the following procedure and is the same as Composition Bin example I: 8.0 parts potassium hydroxide was dissolved in water, 9.2parts glacial acetic acid and 82.8 parts propylene glycol were addedwhile stirring. To a 60:40 ratio of propylene glycol to acetate (4.7parts sodium hydroxide and 14.0 parts potassium hydroxide) composition,11.2 percent by weight of the total additive of a sulfonated lignin and18.7 percent by weight of the total additive of triethanolamine wereadded to give Composition F." Composition G" was made according to theprocedure of example l by mixing 20.4 parts by weight propylene glycolwith 33.0 parts by weight sodium acetate and thereafter adding 13.6parts by weight trlethanolamine, 23.0 parts by weight urea and 10.0parts by weight sulfonated lignin.

The results in the above table show the superiority of additivecompositions of the instant invention when compared to a blank,propylene glycol additive, and a leading commercial additive. Forcomparative purposes, a Blaine fineness of 4,200 (sq. cmJgm.) wasreached in under 40 minutes of grinding time when using Composition F,"whereas in order to get the same fineness the grinding time of a blankof the same clinker was over 80 minutes. Grinding time for the clinkerwith propylene glycol added was over 70 minutes and for the commercialadditive was over 60 minutes. Such improvement in grinding efficiency isvitally important to the commercial producer as it means increasedsaving in power consumption and time. The improvement in pack set indexwas also quite notable as the pack set index of the blank was 12.2 andthe pack set index of Composition "F" was 5.2, which is, of course, asignificant inhibition.

Another important factor, air content, stayed about the same varyingbetween 8.5 percent for Composition C" of example to 9.6 percent for theblank to 10.6 for Composition 6" of example l1. As shown by the table,improvement in compressive strength was somewhat better when usingcompositions of this invention than when no additive was used.

A propylene glycol-acetate-triethanolamine-sulfonated lignin compositionmade according to the procedure set forth in example 11 was produced forexperimental use in a commercial plant handling a Portland-type lcement. This formulation was added as a solution of 10 percent solids ata rate of 1.6 ounces per barrel of cement (0.026 percent solids content)and compared to a blank. The production increased from to 105 barrelsper hour. The pack set index for the blank was whereas the additiveinhibited pack set to a pack set index of 7. The compressive strengthswere significantly the same and the air content of the inventioncomposition increased only slightly. Another important factor is thatthe grinding mill producing the blank at 90 bbL/hr. had a 600 percentcirculating load, whereas the grinding aid reduced the circulating loadto 400 percent. This reduction in circulating load is vitally importantto the cement producer in terms of power consumed.

, Experimental use of the above composition in another commercialplant-handling type I cement resulted in average production increase offrom 210 barrels per hour to 215 barrels per hour over the use of thecommercial additive of examplell.

As noted from the above examples the compositions of this inventionprovide excellent additives for use in grinding hydraulic cements and ininhibiting pack set. While a wide range of combinations may be employedin the scope of this invention, these combinations, in order to achievethe desired results, must be water-soluble and water-dilutable to lowsolids content, e.g., about 10 percent solids. The compositions may beused with equal ease from a ratio of 20 parts by weight polyol to onepart by weight salt of an aliphatic acid having no more than threecarbons to one part by weight polyol to 20 parts by weight of said salt,economics and the particular clinker being the determining factors. Thecompositions of 4 this invention may be effectively used on any type ofcement clinker. These compositions are most conveniently prepared assolutions in water and are generally used at low solids content, withthe preferred composition being a glycol-acetate.

The glycol-acetate-triethanolamine-lignin compositions andglycol-acetate-triethanolaminerligninurea compositions give betterresults than glycol-acetate combinations used alone. The amount oftriethanolamine or equivalent catalyst or accelerator may be from 0 to75 percent by weight of the polyol and triethanolamine combined. Thepreferable amount being 10 to 50 percent by weight. The amount ofsulfonated lignin is determined primarily by permissible amount of airentrainment in the resulting cement and by the viscosity of theadditive. The above factors limit the amount of sulfonated lignin up toa maximum of 50 percent by weight of the total additive. The preferredrange being 10 to 30 percent, because viscosity of the additives withinthis range are easier to handle. The total amount of urea may be from 0to 50 percent by weight of the total additive with the preferred range'being from 0 to 25 percent by weight of the total additive. When urea isused in amounts over 50 percent, the grinding efficiency of theformulation tends to decrease to a point at which eventually thecomposition is no longer an effective grinding aid.

While the invention has been described and illustrated herein byreferences to various specific materials, procedures, and examples, itis understood that the invention is not restricted to the particularmaterials, combinations of materials, and procedures selected for thatpurpose. Numerous variations of such details can be employed, as will beappreciated by those skilled in the art.

We claim:

1. A Portland cement additive composition consisting of a water-solubleglycol and a water-soluble alkali metal salt of an aliphatic acid havingno more than three carbons, said glycol and said salt being employed ina weight ratio of 1:9 to 9:1 respectively, to 50 percent by weight ofthe total additive composition being a water-soluble salt of asulfonated lignin, 0 to 75 percent by weight of a water-solublehydroxy-alkyl amine based on the combined weight of said glycol and saidamine, and 0 to 50 percent by weight based on the total weight of saidadditive composition of urea.

2. The Portland cement additive composition of claim 1 wherein saidwater-soluble glycol is selected from the group consisting essentiallyof monoethylene glycol, polyethylene glycols, monopropylene glycol,polypropylene glycols and mixtures thereof, said water-soluble salt isselected from the group consisting of sodium acetate, potassium acetateand mixtures thereof, and said amine is triethanolamine.

3. The additive of claim 1 wherein said composition is in an aqueoussolution.

4. A Portland cement additive composition consisting essentially of:

a. a water-soluble glycol from the group consisting of monoethyleneglycol, polyethylene glycols, monopropylene glycols, polypropyleneglycols and mixtures thereof and a water-soluble salt from the groupconsisting of sodium acetate, potassium acetate and mixtures thereof,the ratio of said glycol and said salt being employed in a weight ratioof 9:1 to 1:9 respectively,

b. 10 to 30 percent by weight of the total additive composition being awater-soluble salt of a sulfonated lignin,

c. 10 to 50 percent by weight of triethanolamine based on the combinedweight ofsaid glycol and said amine, and

d. O to 25 percent by weight based on the total weight of said additivecomposition of urea.

5. The cement additive of claim 4 wherein said water-soluble salt isformed by reacting acetic acid and a member of the group consisting ofpotassium hydroxide, sodium hydroxide and mixtures thereof.

6. A Portland cement additive composition consisting essentially of:

a. a polypropylene glycol and an acetate from the group consistingessentially of sodium acetate. potassium acetate and mixtures thereofsaid glycol and acetate being employed in a 1.5:] weight ratiorespectively,

b. I 1.2 percent by weight of the total additive composition being awater-soluble sulfonated lignin, and

c. 18.7 percent by weight of the total additive composition beingtriethanolamine.

7. A Portland cement composition containing from about 0.005 to 1.0percent of an additive consisting essentially of a water-soluble glycoland a water-soluble alkali metal salt of an aliphatic acid having nomore than three carbons, the ratio of glycol to salt being employed in aweight ratio of 1:9 to 9: l 0 to 50 percent by weight of the totaladditive being a watersoluble salt ofa sulfonated lignin, 0 to 75percent by weight of a water-soluble hydroxy-alkyl amine based on thecombined weight of said glycol and said amine, and 0 to 50 percent byweight based on the total weight of said additive of urea.

8. A Portland cement composition containing as an essential ingredientfrom about 0.1 to 0.5 percent by weight of an additive consistingessentially of: v

a. a water-soluble glycol from the group consisting of monoethyleneglycol, polyethylene glycols, monopropylene glycols, polypropyleneglycols and mixtures thereof and a water-soluble salt from the groupconsisting of sodium acetate, potassium acetate and mixtures thereof,the ratio of said glycol and said salt being employed in a weight ratioof between 9:1 to 1:9,

b. 10 to 30 percent by weight of the total additive being awater-soluble salt of a sulfonated lignin,

c. 10 to 50 percent by weight of triethanolamine based on the combinedweight of said glycol and said amine, and

d. 0 to 25 percent by weight based on the total weight of said additiveof urea. g 9. The Portland cement composition of claim 8 wherein saidglycol is a polypropylene glycol and the weight ratio of said glycol andsaid salt is 1.5: 1.

10. A process for increasing the grinding efficiency of Portland cementand for inhibiting the pack set of said cement which comprises,intergrinding with said cement from 0.005 to 1.0 percent by weight ofcement of an additive consisting essentially of, a water-soluble glycoland a water-soluble salt of an aliphatic acid having less than threecarbons, the ratio of said glycol to said salt being employed in aweight ratio of 1:9 to 9: l from 0 to 50 percent by weight of the totaladditive of a water-soluble sulfonated lignin, from 0 to 75 percent byweight of a water-soluble hydroxy alkylamine based on the weight of saidglycol and said amine, and from 0 to 50 percent by weight based on thetotal weight of said additive of urea.

11. A process for increasing the grinding eliiciency of Portland cementand for inhibiting the pack set of said cement which comprises,intergrinding with said cement from 0.1 to 0.5 percent by weightofcement ofan additive consisting of,

a. a water-soluble glycol from the group consisting of monoethyleneglycol, polyethylene glycols, monopropylene glycols, polypropyleneglycols and mixtures thereof and a water-soluble salt from the groupconsisting of sodium acetate, potassium acetate and mixtures thereof,the ratio of said glycol and said salt being employed at a weight ratioof between 9:1 and 1:9,

b. from 10 to 30 percent by weight of the total additive being awater-soluble salt of a sulfonated lignin,

c. from 10 to 50 percent by weight triethanolamine based on the combinedweight of said glycol and said amine, and

d. from 0 to 25 percent by weight based on the total weight of saidadditive of urea.

12. The process of claim 11 wherein said glycol is a polypropyleneglycol and the weight ratio of said glycol to said salt is 1.5:l.

2. The Portland cement additive composition of claim 1 wherein saidwater-soluble glycol is selected from the group consisting essentiallyof monoethylene glycol, polyethylene glycols, monopropylene glycol,polypropylene glycols and mixtures thereof, said water-soluble salt isselected from the group consisting of sodium acetate, potassium acetateand mixtures thereof, and said amine is triethanolamine.
 3. The additiveof claim 1 wherein said composition is in an aqueous solution.
 4. APortland cement additive composition consisting essentially of: a. awater-soluble glycol from the group consisting of monoethylene glycol,polyethylene glycols, monopropylene glycols, polypropylene glycols andmixtures thereof and a water-soluble salt from the group consisting ofsodium acetate, potassium acetate and mixtures thereof, the ratio ofsaid glycol and said salt being employed in a weight ratio of 9:1 to 1:9respectively, b. 10 to 30 percent by weight of the total additivecomposition being a water-soluble salt of a sulfonated lignin, c. 10 to50 percent by weight of triethanolamine based on the combined weight ofsaid glycol and said amine, and d. 0 to 25 percent by weight based onthe total weight of said additive composition of urea.
 5. The cementadditive of claim 4 wherein said water-soluble salt is formed byreacting acetic acid and a member of the group consisting of potassiumhydroxide, sodium hydroxide and mixtures thereof.
 6. A Portland cementadditive composition consisting essentially of: a. a polypropyleneglycol and an acetate from the group consisting essentially of sodiumacetate, potassium acetate and mixtures thereof said glycol and acetatebeing employed in a 1.5:1 weight ratio respectively, b. 11.2 percent byweight of the total additive composition being a water-solublesulfonated lignin, and c. 18.7 percent by weight of the total additivecomposition being triethanolamine.
 7. A Portland cement compositioncontaining from about 0.005 to 1.0 percent of an additive consistingessentially of a water-soluble glycol and a water-soluble alkali metalsalt of an aliphatic acid having no more than three carbons, the ratioof glycol to salt being employed in a weight ratio of 1:9 to 9:1, 0 to50 percent by weight of the total additive being a water-soluble salt ofa sulfonated lignin, 0 to 75 percent by weight of a water-solublehydroxy-alkyl amine based on the combined weight of said glycol and saidamine, and 0 to 50 percent by weight based on the total weight of saidadditive of urea.
 8. A Portland cement composition containing as anessential ingredient from about 0.1 to 0.5 percent by weight of anadditive consisting essentially of: a. a water-soluble glycol from thegroup consisting of monoethylene glycol, polyethylene glycols,monopropylene glycols, polypropylene glycols and mixtures thereof and awater-soluble salt from the group consisting of sodium acetate,potassium acetate and mixtures thereof, the ratio of said glycol andsaid salt being employed in a weight ratio of between 9:1 to 1:9, b. 10to 30 percent by weight of the total additive being a water-soluble saltof a sulfonated lignin, c. 10 to 50 percent by weight of triethanolaminebased on the combined weight of said glycol and said amine, and d. 0 to25 percent by weight based on the total weight of said additive of urea.9. The Portland cement composition of claim 8 wherein said glycol is apolypropylene glycol and the weight ratio of said glycol and said saltis 1.5:1.
 10. A process for increasing the grinding efficiency ofPortland cement and for inhibiting the pack set of said cement whichcomprises, intergrinding with said cement from 0.005 to 1.0 percent byweight of cement of an additive consisting essentially of, awater-soluble glycol and a water-soluble salt of an aliphatic acidhaving less than three carbons, the ratio of said glycol to said saltbeing employed in a weight ratio of 1:9 to 9: 1, from 0 to 50 percent byweight of the total additive of a water-soluble sulfonated lignin, from0 to 75 percent by weight of a water-soluble hydroxy alkylamine based onthe weight of said glycol and said amine, and from 0 to 50 percent byweight based on the total weight of said additive of urea.
 11. A processfor increasing the grinding efficiency of Portland cement and forinhibiting the pack set of said cement which comprises, intergrindingwith said cement from 0.1 to 0.5 percent by weight of cement of anadditive consisting of, a. a water-soluble glycol from the groupconsisting of monoethylene glycol, polyethylene glycols, monopropyleneglycols, polypropylene glycols and mixtures thereof and a water-solublesalt from the group consisting of sodium acetate, potassium acetate andmixtures thereof, the ratio of said glycol and and said salt beingemployed at a weight ratio of between 9:1 and 1:9, b. from 10 to 30percent by weight of the total additive being a water-soluble salt of asulfonated lignin, c. from 10 to 50 percent by weight triethanolaminebased on the combined weight of said glycol and said amine, and d. from0 to 25 percent by weight based on the total weight of said additive ofurea.
 12. The process of claim 11 wherein said glycol is a polypropyleneglycol and the weight ratio of said glycol to said salt is 1.5:1.